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Nanoscale zero-valent iron-impregnated

agricultural waste as an effective biosorbent for
the removal of heavy metal ions from
wastewater

Article · January 2017

DOI: 10.1186/s40689-016-0014-5

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Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
DOI 10.1186/s40689-016-0014-5

RESEARCH Open Access

Nanoscale zero-valent iron-impregnated

agricultural waste as an effective
biosorbent for the removal of heavy metal
ions from wastewater
P. Senthil Kumar*, A. Saravanan, P. Sundar rajan and M. Yashwanthraj

Abstract
A novel, nanoscale zero-valent iron-impregnated cashew nut shell (NZVI-CNS) was synthesized towards the removal
of Ni(II) ions from aqueous solution using impregnation procedure. The factors affecting Ni(II) ion adsorption in a
batch mode were studied including the initial metal ion concentration, solution pH, temperature, adsorbent dosage,
and contact time. The adsorption isotherm and kinetics could be described well with Freundlich and pseudo first-
order, respectively. The maximum monolayer adsorption capacity for the removal of Ni(II) ions was found to be
70.05 mg/g. The calculated thermodynamic parameters showed that the removal of Ni(II) ions by the NZVI-CNS was
spontaneous, feasible, and exothermic in nature. The amount of adsorbent needed to treat the known volume of the
effluent was calculated by using single-stage batch adsorber design. The experimental results specifies that the NZVI-
CNS have a high adsorption capacity for the removal of Ni(II) ions from aqueous solution.
Keywords: Adsorption, NZVI-CNS, Freundlich model, Pseudo first-order kinetics, Exothermic, Batch adsorber design

Background hepatitis, infertility, lung cancer, stomatitis, gingivitis, in-

In recent decades, industrialization and urbanization
have grown exponentially to meet the human needs. As
a result, the environmental impact has been increasing
dramatically due to the direct discharge of toxic effluent
into the water bodies. The toxic substances are mostly
hazardous to human health which includes heavy metals,
pharmaceuticals, pesticides, and dyes. Among which,
heavy metals received a special attention by many re-
searchers because they are persistent nature due to lack
of biodegradability (Martins et al. 2013; Singh and Das
2013; Gong et al. 2013). In recent years, these heavy
metals play a vital role in most of the industries. Particu-
larly, nickel is widely used in diverse metal products and
processes. Few of their applications are in industries
such as electroplating, batteries manufacturing, mining,
metal finishing, porcelain enameling, and paint formula-
tions. The toxicity of nickel ions will cause severe health
issues such as dermatitis, allergies, renal disturbances,
* Correspondence: senthilkumarp@ssn.edu.in
Department of Chemical Engineering, SSN College of Engineering, Chennai
603 110, India
somnia, nauseas, and different poisoning degrees to the
kidney and cardiovascular system (Paulino et al. 2007;
Fu et al. 2015; Jeon and Cha 2015). Hence, the effluents
with nickel ions should be treated before letting them
into the receiving water bodies. According to the US
EPA, the permissible limit of nickel in wastewater efflu-
ent is 2 mg/L for short-term effluent reuse and 0.2 mg/L
for long-term effluent reuse (El-Sadaawy and Abdelwa-
hab 2014; U.S EPA 2004). According to the Bureau of
Indian Standards, the maximum permissible limit for
Ni(II) ions in drinking water has been fixed at 0.02 mg/L
(BIS 1994). Therefore, many technologies such as chem-
ical precipitation (Purkayastha et al. 2014), ion exchange,
electrochemical technologies (Fu and Wang 2011), ad-
sorption (Bilal et al. 2013), and membrane filtration
process such as microfiltration (Tashvigh et al. 2015), re-
verse osmosis (Wei et al. 2014), ultrafiltration (Tanhaei
et al. 2014), nanofiltration (Alzahrani and Mohammad
2014), and electrodialysis (Dermentzis 2010) have been
employed for both removal and recovery of Ni(II) ion
from aqueous environment. Most of these technologies

© 2016 Kumar et al. Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0
International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and
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Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
are expensive and incompatibility to remove the trace
level of heavy metal ions. Among these technologies,
many researchers focused on adsorption technology
which offers simplicity, technical feasibility, economical
viability, and social acceptability and also got high re-
moval efficiency of heavy metal from aqueous solution.
On the other hand, the main advantage of this process
is reversible, because the adsorbents used for metal
ions removal can be regenerated by employing appro-
priate desorption process (Barakat 2011; Zhou et al.
2015; Mahmoud et al. 2015). The commercial adsorb-
ent such as activated carbons (Rajkumar et al. 2014),
polymeric materials (Anitha et al. 2015), clays (Lee and
Tiwari 2012), biosorbents (Kumar et al. 2015), and
other adsorbents have been commonly used for this ad-
sorption process. Many adsorbents usually have lower
adsorption capacity, higher cost, longer equilibrium
time, poor regeneration abilities, and separation prob-
lems (Prabu et al. 2015, 2016). Hence, adsorbents
qualifying the aforementioned problems were synthe-
sized and employed for removal of metal ions from
aqueous environment.
Nanoscale zero-valent iron (NZVI) is a promising
technology because many researchers focused on this
process and implemented in the treatment of hazardous
contaminants from wastewater. This increase in interest
on the use of NZVI is owing to its higher surface area,
lower cost, non-toxic, and higher reactivity (Uzum et
al. 2009; Boparai et al. 2011; Arshadi et al. 2014;
Prabu et al. 2016). The removal mechanism is direc-
tional transfer of electrons from NZVI to the contam-
inants and then the contaminant is transformed into
non-toxic or less-toxic species. In addition, it also de-
grades and oxidize the organic compounds in the
presence of dissolved oxygen (DO) (Fu et al. 2014;
Prabu et al. 2015, 2016). Mostly, direct of use of
NZVI is restricted due to its lack of stability, easy ag-
gregation, and facing difficulties in separating NZVI
from treated effluents. To mitigate these issues, NZVI
is impregnated with supporting material such as
cashew nut shell (CNS) with the help of sonication
operation. This does not only provide better operation
but enhances the reduction ability of NZVI (Fu et al.
2014; Prabu et al. 2016). Finally, the efficient removal
of nickel ions in aqueous environment can be
achieved by utilizing the synthesized nanoscale zero-
valent iron-impregnated cashew nut shell (NZVI-
CNS). In this research, the batch adsorption studies
for the removal of Ni(II) ions were investigated by
using the several parameters such as initial Ni(II)
concentration, solution pH, temperature, adsorbent
dose, and contact time. The adsorption isotherm, kin-
etics, design, and thermodynamic studies have been
discussed to explain the adsorption process.
Page 2 of 11
Methods
Chemicals and equipment
The chemical nickel(II) sulfate hexahydrate [NiSO4·6H2O]
was used to prepare the stock solution of Ni(II) ions. The
nickel salt was taken in a measured amount and diluted
in double distilled water. To make the desired Ni(II)
ions concentration solution (25–150 mg/L), the stock
solution was further diluted with distilled water. The
pH of the different ion concentration solution was mea-
sured with a pH meter (Elico Limited, India) and was
adjusted using 0.1 N NaOH and 0.1 N HCL solutions.
The concentration of Ni(II) ions onto the ions solution
before and after adsorption process was measured with
an atomic adsorption spectrophotometer (AAS, SL 176
Model, Elico Limited, Chennai, India).
Preparation of the adsorbent
The adsorbent was prepared by simple liquid-phase re-
duction process, which is that NZVI was impregnated
with the adsorbent material—CNS. One gram of CNS
powder was washed with water to remove the impurities
and then soaked in saturated FeSO4·7H2O solution
(6.5 g in 25 mL with two drops of concentrated sulfuric
acid) for 30 min. After that, the soaked CNS along with
the saturated FeSO4·7H2O solution was continuously son-
icated with the ultrasonic working frequency of 24 kHz
and mechanically agitated with the speed of 500 rpm/min
for 60 min. During the sonication process, the CNS parti-
cles were broken into small pieces under the thermo-
dynamic condition. After the sonication, 0.1 mol/L NaBH4
was slowly added to the solution at optimum pressure,
temperature, and atmosphere. Finally, the ferrous ion was
impregnated into the CNS particles, and the ferrous ion
was reduced to ZVI as per the −following reaction.
− 2Feo
ðaqÞ þ BH4ðaqÞ þ 2H2 O þ support→
2Fe2þ
supportðsÞ
þ BO−2ðaqÞ þ 4Hþ
ðaqÞ þ 2H2 ðgÞ:
ð1Þ
The CNS system was completely washed using dis-
tilled water followed by a wash with methanol to prevent
the corrosion formation. At last, the CNS system was
dried and stored in an oxygen-free nitrogen environ-
ment. This prepared material was abbreviated as NZVI-
CNS (NZVI-impregnated CNS). During the synthesis of
ZVI, the particles of boron were formed. These particles
are toxic in nature, so special care must be needed for
separating the boron particles.
Batch adsorption studies
The batch adsorption studies were performed to optimize
the parameters such as initial Ni(II) concentration,
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
solution pH, temperature, adsorbent dose, and contact
time on the effective removal of the Ni(II) ions from the
aqueous solution using the NZVI-CNS. One hundred mil-
liliters of the Ni(II) ion solution with varying concentra-
tions (25–150 mg/L), adsorbent dosages (0.5–3.0 g/L),
solution pH (2.0–8.0), contact times (5–60 min), and tem-
peratures (30–60 °C) was taken in 100 mL Erlenmeyer
flasks and then the mixture was kept in a temperature-
controlled rotary shaker. The mixture was withdrawn at
different time intervals (0–60 min). The concentration of
the residual metal ions in the solutions was measured
using an atomic adsorption spectrophotometer (AAS) (SL
176 Model, Elico Limited, Chennai, India). The percentage
removal of the Ni(II) ion was calculated by using the fol-
lowing equation:
C o −C e
% Removal of metal ions ¼  100;
Co
where Co (mg/L) and Ce (mg/L) are the initial and
equilibrium concentrations of Ni(II) ion solution,
respectively.
Adsorption equilibrium experiments
The adsorption isotherm studies were performed in a
series of 100 mL Erlenmeyer flasks by adding 0.2 g of
adsorbent material (NZVI-CNS) into 100 mL of the
Ni(II) ion solution with the various initial Ni(II) ion con-
centrations in the range of 25 to 150 mg/L at an
optimum condition, and then, the mixtures were kept in
a temperature-controlled shaking incubator until its
equilibrium time. Once the equilibrium time is reached,
the flasks were withdrawn from the incubation shaker
and the adsorbent material NZVI-CNS was centrifuged
to separate the supernatant and the spent adsorbent.
The concentration of Ni(II) ion in the supernatant was
examined by using atomic adsorption spectrophotom-
eter (AAS) (SL 176 Model, Elico Limited, Chennai,
India), and the values are substituted in the following
formula to know the amount of Ni(II) ion adsorbed onto
the NZVI-CNS at equilibrium, qe (mg/g).
The amount of Ni(II) ions adsorbed at equilibrium qe
(mg/g)
ðC o −C e ÞV
qe ¼ ; ð3Þ
m qe ¼
where Co and Ce are the concentrations of Ni(II) ions
in the solution initially and at equilibrium (mg/g), re-
spectively, V is the volume of the Ni(II) ion solution (L),
and m is the mass of the adsorbent (g).
The two-parameter and the three-parameter isotherm
models were used to explain the Ni(II) ions adsorption to-
wards the selected adsorbent. The different parameters,
Page 3 of 11
R2, and the error values are analyzed by the MATLAB
R2009a software.
Langmuir (1918) and Freundlich (1906) are the two-
parameter isotherm models used in this study.
The non-linear form of Langmuir adsorption isotherm
model is as follows (Langmuir 1918):
qm K L C e
qe ¼ ; ð4Þ
1 þ K LCe
where qe is the adsorption capacity at equilibrium
(mg/g), qm is the maximum monolayer adsorption cap-
acity (mg/g), Ce is the concentration of the metal ions at
equilibrium (mg/L), and KL is the Langmuir equilibrium
constant (L/mg).
The Freundlich adsorption model as follows (Freundlich
1906):
ð2Þ
qe ¼ K F C e=n ;
1
ð5Þ
where Ce is the concentration of the metal ions at
equilibrium (mg/L), KF is the Freundlich constant [(mg/
g)(L/mg)(1/n)] related to the bonding energy, and n is a
measure of deviation from the linearity of adsorption (g/
L). The significance of “n” is as follows: n = 1 (linear),
n > 1 (physical process), and n < 1 (chemical process).
Redlich and Peterson (1959) and Sips (1948) are the
three-parameter isotherm models used in this study.
The Redlich-Peterson isotherm model is given as fol-
lows (Redlich and Peterson 1959):
!
K RP C e
qe ¼ ; ð6Þ
1 þ αRP C βe RP
where Ce is the concentration of metal ions at equilib-
rium (mg/L), βRP is the exponent which lies between 0
and 1, KRP is the Redlich-Peterson isotherm constant (L/
g), αRP is the Redlich-Peterson isotherm constant (L/
RP . The significance of β is as given as follows: β = 1
mg)1/β
(Langmuir adsorption isotherm model is a preferable ad-
sorption isotherm model) and β = 0 (Freundlich adsorp-
tion isotherm model is a preferable adsorption isotherm
model).
The Sips adsorption isotherm model is given as follows
(Sips 1948):
!
K S C βe s
; ð7Þ
1=
β
1 þ αS C e s
where Ks is the Sips model isotherm constant (L/g)βS,
αs is the Sips model constant (L/g)1/βS, and βS is often
regarded as the heterogeneity factor, with values close to
1 indicating a homogeneous binding site and values
greater than 1 indicating a heterogeneous adsorption
system.
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
Adsorption kinetic experiments
The adsorption kinetic studies were performed in a
series of 100 mL Erlenmeyer flasks by varying the con-
tact time from 0 to 60 min of the adsorbent with the dif-
ferent initial Ni(II) ion solutions (25–150 mg/L) along
with the adsorbents and kept in a temperature-
controlled shaking incubation. At predetermined time
intervals, the flasks were withdrawn from the incubation
shaker, the adsorption mixture was centrifuged to separ-
ate the supernatant and the spent adsorbent. The con-
centration of Ni(II) ion in the supernatant was examined
by using atomic adsorption spectrophotometer (AAS)
(SL 176 Model, Elico Limited, Chennai, India), and the
values are substituted in the following formula to know
the amount of Ni(II) ion adsorbed onto the NZVI-CNS
at different time intervals, qt (mg/g).
ðC o −C t Þ V
qt ¼ ; ð8Þ
m of ΔSo and ΔHo were calculated from the slope and the
where qt is the amount of Ni(II) ions adsorbed by the
adsorbent at any time (mg/g), Ct is the concentration of
Ni(II) ions at particular time (mg/L), V is the volume of
the metal ion solution (L), and m is the mass of the ad-
sorbent (g).
The pseudo first-order, pseudo second-order, and Elo-
vich kinetic models are used to determine the rate of the
adsorption process.
Pseudo first-order kinetic model is given as follows
(Lagergren 1898):
qt ¼ qe ð1− expð−k 1 t ÞÞ;
where qt is the adsorption capacity at any time (mg/g),
qe is the equilibrium adsorption capacity (mg/g), k1 is
the pseudo first-order kinetic rate constant (min−1), and
t is the time (min).
Pseudo second-order kinetic model is given as follows
(Ho and McKay 1999):
q2e k 2 t
qt ¼ ; ð10Þ
1 þ qe k 2 t
where k2 is the pseudo second-order kinetic rate con-
stant (g/mg min) and t is the time (min).
Elovich kinetic model is given as follows (Low 1960):
qt ¼ ð1 þ βE Þ lnð1 þ αE βE t Þ;
where βE is the desorption constant related to the acti-
vation energy of chemisorption (g/mg) and αE is the ini-
tial adsorption rate (mg/(g min)).
Adsorption thermodynamic study
The adsorption thermodynamics studies were performed
by varying the temperature of the batch adsorption sys-
tem from 303 to 333 K. The adsorption process is
Page 4 of 11
explained by the thermodynamic parameters like Gibbs
free energy (ΔGo, kJ mol−1), enthalpy (ΔHo, kJ mol−1),
and entropy (ΔSo, kJ mol−1) which was calculated from
the following equations:
C Ae
Kc ¼ ð12Þ
Ce
ΔGo ¼ −RT lnK c ð13Þ
ΔGo ¼ ΔH o −T ΔS o ð14Þ
ΔS o ΔH o
logK c ¼ − ; ð15Þ
2:303R 2:303RT
where CAe is the amount of Ni(II) ions adsorbed onto
the adsorbent per liter of solution at equilibrium (mg/L),
Ce is the equilibrium concentration in solution (mg/L), T
is the temperature (K), R is the gas constant (8.314 J/
mol/K), and Kc is the equilibrium constant. The values
intercept of the plot of log Kc versus 1/T.
Results and discussions
Equilibrium studies
Influence of initial Ni(II) ion concentration on the
adsorption of Ni(II) ions and adsorption isotherms
The effect of initial Ni(II) ions concentration on the ad-
sorption of Ni(II) ions is the main important parameter
for resolving the adsorption capacity of the adsorbent. In
this study, the effect of Ni(II) ion concentration was
studied with the range of nickel ion concentration = 25–
ð9Þ 150 mg/L, solution pH = 5.0, adsorbent dose = 2 g/L, vol-
ume of sample = 100 mL, equilibrium time = 30 min,
temperature 30 °C, and the results were shown in Fig. 1.
The experimental results showed that the percentage re-
moval of Ni(II) ion was decreased from 99.72 to 87.89 %
with an increase in initial Ni(II) ion concentration from
25 to 150 mg/L. Adsorption is a surface phenomenon,
ð11Þ
Fig. 1 Effect of initial Ni(II) ion concentration on the removal of
Ni(II) ions by NZVI-CNS (nickel ion concentration = 25–150 mg/L,
solution pH = 5.0, adsorbent dose = 2 g/L, volume of sample = 100 mL,
equilibrium time = 30 min, temperature 30 °C)
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3 Page 5 of 11

the surface saturation of metal ions strongly depends on models. The adsorption isotherm data for the removal of
the initial metal ion concentrations. The initial concen- Ni(II) ions onto the NSZV-CNS was constantly fitted with
tration affords an essential driving force to conquer all the Freundlich isotherm model which indicates that the
mass transfer resistance of metal ions between the liquid adsorption process was the heterogeneous nature of active
phase and the solid phase. At low metal ion concentra- sites on the surface of the NSZV-CNS, a multilayer ad-
tion, the availability of surface active sites might be high, sorption occurred between the adsorbent material NSZV-
i.e., the ratio of active sites to the metal ions in the aque- CNS and the Ni(II) ions in the liquid solution (Jiang et al.
ous solution is higher, therefore all the metal ions may 2012). The values of n that were determined from the
be occupied on the active sites of the adsorbent (Li et al. Freundlich isotherm model were found to be 2.956 for
2013). The drop off of removal percentage might be due NSZV-CNS; the value of n lies between 1 and 10, which
to the saturation of available active sites at higher concen- indicates that the adsorption of Ni(II) ions onto the
tration. The adsorption capacity of NSZV-CNS was in- NSZV-CNS was physical adsorption. Based on the correl-
creased from 12.46 to 65.92 mg/g, due to the higher ation coefficient values, the experimental data gave estim-
adsorption rate and the exploitation of all available bind- able fits within the following isotherm order: Freundlich >
ing sites for adsorption at higher Ni(II) ion concentration. Sips > Redlich-Peterson > Langmuir.
The obtained equilibrium data from the effect of
Ni(II) ion concentration studies were evaluated by Influence of solution pH on the adsorption of Ni(II) ions
using several adsorption isotherm model which can be The pH value of the aqueous solution plays a significant
used for the design of an adsorption system. In this role in the adsorption process which affects the binding
study, Langmuir (Langmuir 1918), Freundlich (Freundlich sites and chemical interaction between the metal ions
1906), Redlich-Peterson (Redlich and Peterson 1959), and and the adsorbents via changing the ionization state of
Sips (Sips 1948) isotherm model were used to calculate the functional groups present on the surface of the ad-
the maximum monolayer adsorption capacity of NSZV- sorbent. In order to find out the optimum pH, the effect
CNS and the equilibrium data for the adsorption of Ni(II) of solution pH for the removal of Ni(II) ions by NZVI-
ions from aqueous solution; the results were shown in CNS was deliberated over the range of solution pH =
Fig. 2. The Langmuir constant (KL) and the monolayer ad- 2.0–8.0, adsorbent dose = 2 g/L, volume of sample =
sorption capacity (qm), the Freundlich isotherm constant
(KL) and n, the Redlich-Peterson isotherm constant (KRP Table 1 Isotherm constants of the two-parameter and three-
and αRP) and βRP, and the Sips model constant (KS and αS) parameter models for the removal of Ni(II) ions by NZVI-CNS
and βS were determined using the plot Ce and qe. The ad- Parameters Values R2
sorption isotherm parameters, determination of coefficient Two-parameter models
values (R2), and error values (sum of squared errors (SSE),
Langmuir model qm (mg/g) 70.05 0.9276
root mean squared values (RMSE)) were attained by fitting
the adsorption isotherm data to the adsorption isotherm KL (L/mg) 0.3577
models are shown in Table 1. As it can be seen in Table 1, SSE 203.4
Freundlich adsorption isotherm models have high correl- RMSE 7.131
ation coefficient value (R2 = 0.9901) and low error values Freundlich model KF [(mg/g)(L/mg)(1/n))] 23.88 0.9901
(SSE = 27.77, RMSE = 2.635) compared to other isotherm n (g/L) 2.956
SSE 27.77
RMSE 2.635
Three-parameter models
Redlich-Peterson model KRP (L/g) 64.64 0.9613
αRP (L/mg)(1/βRP) 2.011
βRP 0.7487
SSE 108.7
RMSE 5.214
Sips model KS (L/g)βs 21.76 0.9848
αs (L/mg) (βs)
1.798
βS 0.3806

Fig. 2 Adsorption isotherm studies for the removal of Ni(II) ions SSE 40.31
by NZVI-CNS RMSE 3.174
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
100 mL, equilibrium time = 30 min, temperature 30 °C
with a nickel ions concentration = 25 mg/L. Figure 3
shows that the percentage removal of Ni(II) ion was in-
creased with the increase of pH value from 2.0 to 5.0.
Beyond the pH value, the adsorption capacity remains
constant due to the occurrence of hydroxyl ions which
causes the arrangement of metal hydroxide complexes,
which decline the adsorption capacity of NZVI-CNS.
Figure 3 shows that the maximum removal of Ni(II) ions
was attained at the solution pH of 5.0 which indicated
that the adsorption capacity of NZVI-CNS was higher at
acidic condition. At acidic condition due to the electro-
static interaction, the negatively charged Ni(II) ions was
adsorbed by the positively charged adsorbent material
NZVI-CNS.
Influence of temperature on the adsorption of Ni(II) ions
and thermodynamic studies
The effect of temperature for the removal of Ni(II) ions
onto the NZVI-CNS was studied by allowing the Ni(II)
ion concentration = 25–150 mg/L, solution pH = 5.0, ad-
sorbent dose = 2 g/L, volume of sample = 100 mL, equi-
librium time = 30 min, temperature 30–60 °C, and the
results were shown in Fig. 4. The results showed that
the percentage removal of Ni(II) ions was decreased with
an increase in the temperature from 30 to 60 °C for the
Ni(II) ion concentration (25–150 mg/L), which indicates
that the adsorption process was exothermic in nature.
At higher temperature, the kinetic energies of Ni(II) ions
was higher. Consequently, the adsorption of high energy
metal ions is not easier compared with low energy ions.
This is probably due to the fading of adsorptive forces
between the metal ions and the binding sites on the sur-
face of the adsorbent material—NZVI-CNS, which
means that the adsorption process is inversely propor-
tional to the temperature (Karami 2013). The thermo-
dynamic behaviors of the adsorption of Ni(II) ions onto
Fig. 3 Effect of solution pH for the removal of Ni(II) ions by NZVI-
CNS (nickel ion concentration = 25 mg/L, solution pH = 2.0–8.0,
adsorbent dose = 2 g/L, volume of sample = 100 mL, equilibrium
time = 30 min, temperature 30 °C)
Page 6 of 11
Fig. 4 Effect of temperature for the removal of Ni(II) ions by NZVI-
CNS (nickel ion concentration = 25–150 mg/L, solution pH = 5.0,
adsorbent dose = 2 g/L, volume of sample = 100 mL, equilibrium
time = 30 min, temperature 30–60 °C)
the NZVI-CNS were analyzed by plotting the graph be-
tween log Kc and 1/T (Fig. 5), and the calculated
thermodynamic parameters such as Gibbs free energy
(ΔGo), enthalpy change (ΔHo), and entropy change (ΔSo)
for the adsorption of Ni(II) ions are shown in Table. 2. It
was found that the negative value of Gibbs free energy
was increased with an increase the temperature from 30
to 60 °C which confirms that the adsorption of Ni(II)
ions onto the NZVI-CNS was more positive at low
temperature and the adsorption process was feasible and
spontaneous in nature (Li et al. 2013). The negative
value of changes in enthalpy (ΔHo) confirm that the ad-
sorption of Ni(II) ion onto the NZVI-CNS was exother-
mic in nature. The negative value of changes in entropy
(ΔSo) indicated that the adsorption of Ni(II) ion onto the
NZVI-CNS was enthalpy driven.
Influence of adsorbent dosage on the adsorption of Ni(II)
ions
Temperature is the significant factor that can influence
the adsorption process. The effect of temperature for the
Fig. 5 Thermodynamic analysis for the removal of Ni(II) ions
by NZVI-CNS
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3 Page 7 of 11

Table 2 Thermodynamic parameters for the adsorption of Ni(II) ions onto NZVI-CNS
Metal Concentration ΔHo ΔSo ΔGo (kJ/mol)
ions of Ni(II) ion (kJ/mol) (J/mol/K)
30 °C 40 °C 50 °C 60 °C
solution
(mg/L)
Ni(II) 25 −61.998 −162.94 −14.846 −10.327 −9.134 −8.143
50 −31.688 −73.52 −9.300 −8.936 −7.790 −7.226
75 −24.699 −55.76 −7.920 −7.152 −6.479 −6.312
100 −13.630 −25.12 −5.979 −5.782 −5.586 −5.200
150 −11.719 −22.15 −4.994 −4.761 −4.653 −4.288

removal of Ni(II) ion was studied by using the optimum
parameters such as Ni(II) ion concentration = 25 mg/L,
solution pH = 5.0, volume of sample = 100 mL, equilib-
rium time = 30 min, temperature 30 °C, and the varied
adsorbent dosage of 0.5–3 g/L, and the results were
shown in Fig. 6. From Fig. 6, it was observed at the per-
centage removal of Ni(II) ions was increased with an in-
crease in the adsorbent dosage from 0.5 to 3 g/L. This
may be possible due to the increase in available binding
sites of the adsorbent with the increase in adsorbent
dosage (Fan et al. 2008). The maximum percentage re-
moval was attained at 2 g/L, beyond that the removal
percentage was almost constant. The equilibrium ad-
sorption capacity (qe) was decreased with the increase in
the adsorbent dosage. The reason for this may be due to
the more availability of binding sites and increase in the
surface area at lower adsorbent dose; therefore, the
metal uptake capacity will be high at lower dosage. Con-
versely, overlying or aggregation of the adsorption sites
at higher dosage (Lata et al. 2008).
Influence of contact time on the adsorption of Ni(II) ions
and kinetic studies
The effect of contact time for the removal of Ni(II) ions
onto the NZVI-CNS was studied with the range of Ni(II)
ion concentration = 25–150 mg/L, solution pH = 5.0, ad-
sorbent dose = 2 g/L, volume of sample = 100 mL,
temperature 30 °C, and contact time = 5–60 min, and
the results were shown in Fig. 7. From the Fig. 7, it was
observed that the percentage removal of Ni(II) ion was
increased with an increase in the contact time from 5 to
60 min. The result affirmed that the percentage removal
of Ni(II) ions onto the NZVI-CNS was increased quickly
at the first 10 min and then increased gradually and
reached adsorption equilibrium at 30 min. The rapid in-
crease of the adsorption of Ni(II) ions at the initial stage
of contact time due to the accessibility of huge amount
of binding sites on the surface of the adsorbent material.
At lesser contact time, the residential time offered for
the adsorption of Ni(II) ion onto the NZVI-CNS is less,
for that reason, the percentage removal of Ni(II) ion is
less. At higher contact time, the rate of adsorption
slowly increased until equilibrium, this might be possibly
due to the destabilization of driving force and the avail-
able binding sites were gradually tapered and taking long
time to reach the adsorption equilibrium. The adsorp-
tion mechanism and the rate at which the Ni(II) ion was
removed from the aqueous solution were estimated by
using adsorption kinetic models. In these study, three
kinetic models such as pseudo first-order (Lagergren

Fig. 6 Effect of adsorbent dose for the removal of Ni(II) ions by Fig. 7 Effect of contact time for the removal of Ni(II) ions by NZVI-
NZVI-CNS (nickel ion concentration = 25 mg/L, solution pH = 5.0, CNS. Nickel ions concentration = 25–150 mg/L, solution pH = 5.0,
adsorbent dose = 0.5–3 g/L, volume of sample = 100 mL, equilibrium adsorbent dose = 2 g/L, volume of sample = 100 mL, contact time =
time = 30 min, temperature 30 °C) 5–60 min, temperature 30 °C
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
1898), pseudo second-order (Ho and McKay 1999), and
Elovich kinetic model (Low 1960) were used to exam-
ine the adsorption kinetics for the removal of Ni(II)
ion onto the NZVI-CNS, and the results were shown
in Fig. 8. The estimated parameters such as pseudo
first-order kinetics constant (k1) and qe, the pseudo
second-order kinetic constant (k2) and qe, and the
Elovich kinetic model constant (αRP) and βRP are
listed in Table. 3. The comparison was made between
the calculated adsorption capacity (qe, cal) and the
experimental adsorption capacity (qe, exp). It can be
seen from Table 3 that the pseudo first-order kinetic
were very closer to the experimental adsorption cap-
acity value (qe, exp) compared with other kinetic
Fig. 8 Adsorption kinetic fit for the removal of Ni(II) ions by NZVI-CNS (nickel ion concentration = 25–150 mg/L, solution pH = 5.0, adsorbent dose =
2 g/L, volume of sample = 100 mL, temperature = 30 °C)
Page 8 of 11
models. Additionally, the determination of correlation
coefficient values for the pseudo first-order kinetic
was higher compared with pseudo second-order and
Elovich kinetic model. The adsorption kinetic data for
the removal of Ni(II) ions onto the NSZV-CNS were
constantly fitted with pseudo first-order kinetic model
which indicates that the physical adsorption is the
rate-determining step (Aliabadi et al. 2013). The pre-
diction of the rate-limiting step is important to
understand the adsorption mechanism. As it can be
seen in Table 2, the values of rate constant “k” de-
creases as the concentration of Ni(II) ion increased;
this might be possibly due to the lower competition
for the binding sites at lower concentration. At higher
Kumar et al. Textiles and Clothing Sustainability (2016) 2:3 Page 9 of 11

Table 3 Adsorption kinetic data for the removal of Ni(II) ions by NZVI-CNS
Adsorption kinetic Parameters Values (mg/L)
model
25 50 75 100 150
Pseudo first-order qe (mg/g) 12.41 24.39 36.13 46.06 66.66
qe, exp (mg/g) 12.47 24.49 36.14 45.95 65.99
k1 (min−1) 0.1305 0.1221 0.1105 0.1089 0.1019
2
R 0.9941 0.9934 0.991 0.9935 0.9933
SSE 1.654 5.199 13.02 14.52 32.25
RMSE 0.3877 0.6875 1.088 1.149 1.712
Pseudo second-order qe, cal (mg/g) 13.97 27.68 41.56 53.19 77.84
k2 (g/mg min) 0.0135 0.006159 0.00353 0.00267 0.00164
R2 0.9912 0.9907 0.99 0.9907 0.9871
SSE 0.9014 3.86 13.63 20.74 62.02
RMSE 0.2863 0.5924 1.113 1.373 2.374
Elovich kinetic model αE mg/(g min) 1.478 2.958 0.272 0.181 0.2491
βE (g/mg) 0.5539 1.128 3.303 4.596 5.872
R2 0.9378 0.9793 0.962 0.9608 0.9679
SSE 9.666 12.59 51.87 87.75 154.1
RMSE 0.8975 1.07 2.079 2.704 3.742

concentration, the competition for the binding sites
will be high and accordingly lower adsorption rates
are attained (Gao et al. 2013).
Design of a single-stage batch adsorber
The best fitted adsorption isotherm model was used to
design the single-stage batch adsorber for the removal
of Ni(II) ions from aqueous solution. A schematic dia-
gram of a single-stage batch adsorber is shown in Fig. 9.
The main objective of the adsorber was to estimate the
amount of adsorbent needed for treating the known
volume and concentration of Ni(II) ions from the aque-
ous solution at optimum condition. The mass balance
for the single-stage batch adsorption system at equilib-
rium condition can be given as follows (at time t = 0,
q0 = 0):
V ðC o −C e Þ ¼ Mðqe −qo Þ; ð16Þ
where M is the mass of the adsorbent (g), V is the vol-
ume of Ni(II) ion solution (L), Co is the initial Ni(II) ion
concentration (mg/L), Ce is the Ni(II) ion concentration
at equilibrium (mg/L), qe is the equilibrium adsorption
capacity (mg/g), and qo is the adsorption capacity at time
t = 0 (mg/g). In this study, the fresh adsorbent was used
for the adsorption system, therefore qo = 0, rearranging
Eq. 16 gave
ðC o −C e Þ
M¼ V: ð17Þ
qe
The Freundlich adsorption isotherm model was best
fitted for the present adsorption system; this model was
included in Eq. 17 and the equation can be written as

Fig. 9 Schematic diagram of a single-stage batch adsorber

Kumar et al. Textiles and Clothing Sustainability (2016) 2:3
ðC o −C e Þ
M¼ V: ð18Þ
K F C 1=n
e
Figure 10 shows the plot of mass of adsorbent versus
volume of the solution of initial Ni(II) ion concentration
of 75 mg/L for 75, 80, 58, 90, and 95 % of Ni(II) ion re-
moval at different solution volumes (1–10 L) for a
single-stage batch adsorber. This design was used to cal-
culate the amount of adsorbent dose needed for the
treatment of known volume of the contaminated water.
For example, the amount of optimum adsorbent dose
needed to treat 10 L of the Ni(II) ion solution with 95 %
removal of 75 mg/L Ni(II) ion solution was found to be
22.27 g of adsorbent.
Conclusions
In summary, we reported that the NZVI-CNS adsorbent
material was successfully synthesized through the im-
pregnated method which have been effectively used for
the removal of Ni(II) ions from aqueous solution. The
adsorption was studied kinetically using diverse adsorp-
tion kinetic models such as pseudo first-order, pseudo
second-order, and Elovich kinetic models. The results
showed that the adsorption process followed the pseudo
first-order model based on higher correlation coefficient
with low error values. The adsorption of Ni(II) ions onto
NZVI-CNS was influenced by several operating parame-
ters such as initial Ni(II) ion concentration, solution pH,
contact time, temperature, and adsorbent loading. The
maximum monolayer adsorption capacity for the re-
moval of Ni(II) ions was found to be 70.05 mg/g at an
optimum condition. The equilibrium isotherm has been
analyzed using different isotherm models such as Lang-
muir, Freundlich, Redlich-Peterson, and Sips model.
Among these, the Freundlich isotherm model was iden-
tified as a well-suitable adsorption isotherm model based
on the high coefficient of determination values with low
error values. The adsorption thermodynamics illustrated
Fig. 10 Batch adsorber design for the removal of Ni(II) ions by NZVI-CNS
Page 10 of 11
that the electrostatic interaction plays an important role
in the adsorption process. The values of thermodynamic
parameters such as Gibbs free energy, entropy, and en-
thalpy indicated that the adsorption process was spon-
taneous, feasible, and exothermic in nature. A batch
adsorber was designed to determine the amount of ad-
sorbent dose needed for the treatment of a known vol-
ume of the desired Ni(II) ion concentration. Based on
the experimental studies, it can be concluded that the
NZVI-CNS materials has more potential for the re-
moval of Ni(II) ions, and correspondingly for many
other heavy metal ions from aqueous solution, with the
advantages of being low cost, recyclable, efficient, and
economically friendly.
Competing interests
The authors declare that they have no competing interests.
Authors’ contributions
PSK have made substantial contributions to the conception and design, or
acquisition of data, or analysis and interpretation of data and also have given
final approval of the version to be published. AS, PSR, and MY have been
involved in drafting the manuscript and revising it critically for important
intellectual content. All authors read and approved the final manuscript.
Received: 16 December 2015 Accepted: 3 March 2016
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